Preparation of allylic compounds

Abstract

Allyl methyl ethers are transetherified with alcohols by use of a catalyst of a solid acid that contains no mercury or cuprous salt catalyst.

What is claimed is: 
     
       1. A process for preparing an allylic compound corresponding to the formula   XHC═CHY     wherein X is RCH 2  -- or RCH 2  CH(OR')-- and Y is --CH 2  OR' or hydrogen, and when X is RCH 2  --, Y is --CH 2  OR' and when X is RCH 2  CH(OR')--, Y is hydrogen, where R is hydrogen or an alkyl moiety having from 1 to about 20 carbons and R' is a C 1-20  moiety corresponding to the formula (CHRCHRO) n  R wherein R is as previously defined and n is an integer from zero to about 10, comprising contacting an allyl methyl ether corresponding to the formula     X'HC═CHY'     wherein X' is RCH 2  -- or RCH 2  CH(OCH 3 )-- and Y' is CH 2  OCH 3  or hydrogen and when X' is RCH 2  --, Y' is --CH 2  OCH 3  and when X' is RCH 2  CH(OCH 3 )--, Y' is hydrogen where R is as previously defined, with a primary or secondary alcohol, or a (poly)alkylene glycol or monoalkyl ether thereof corresponding to the formula HO(CHRCHRO) n  R in the presence of a catalytic amount of a catalyst present in an amount by weight based on allyl methyl ether of from about 0.1 percent to about 10 percent, consisting essentially of a solid heterogeneous strong acid that contains no mercury or cuprous salt catalysts at an elevated temperature such that the allylic compound is produced.   
     
     
       2. A process according to claim 1 wherein the pressure is from about atmospheric to about 1000 psig. 
     
     
       3. A process according to claim 2 wherein the temperature is from about 50° C. to about 200° C. 
     
     
       4. A process according to claim 3 wherein the pressure is from about 50 psig to about 300 psig. 
     
     
       5. A process according to claim 4 wherein the temperature is from about 60° C. to about 150° C. 
     
     
       6. A process according to claim 5 wherein the pressure is from about 100 psig to about 200 psig. 
     
     
       7. A process according to claim 1 conducted in an inert reaction atmosphere. 
     
     
       8. A process according to claim 1 wherein the (poly)alkylene glycol or monoalkyl ether thereof is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and lower alkyl ethers thereof. 
     
     
       9. A process according to claim 1 wherein the allyl methyl ether is selected from the group consisting of 3-methoxy-1-butene, 1-methoxy-2-butene, 3-methoxy-1-pentene, 2-methoxy-3-pentene and mixtures thereof. 
     
     
       10. The process according to claim 1 wherein the catalyst is selected from the group consisting of strong acid-exchanged polymeric ion-exchange resins, acidic clays, acid treated silica, acid treated alumina, and acid form zeolites. 
     
     
       11. A process according to claims 1, 2, 3, 4, 5, 6, 7, 8 or 9 wherein the catalyst is a sulfonated macroporous styrene-divinylbenzene copolymer in the acid form. 
     
     
       12. A process according to claim 1, 3, 5, 2, 4, 6, 7, 8, 9 or 10 wherein the temperature is about 100° C. or above. 
     
     
       13. A process according to claim 12 wherein the catalyst is a sulfonated macroporous styrene-divinylbenzene copolymer in the acid form. 
     
     
       14. A process according to claim 6 wherein (a) the (poly)alkylene glycol or monoalkyl ether thereof is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and lower alkyl ethers thereof;   (b) the allyl methyl ether is selected from the group consisting of 3-methoxy-1-butene, 1-methoxy-2-butene, 3-methoxy-1-pentene, 2-methoxy-3-pentene and mixtures thereof; and   (c) the catalyst is a sulfonated macroporous styrene-divinylbenzene copolymer in the acid form.   
     
     
       15. A process according to claim 14 wherein methanol is removed as a by-product during the course of the reaction. 
     
     
       16. A process according to claim 15 wherein the yield is about 90 percent or above. 
     
     
       17. A process according to claim 14 wherein the temperature is about 100° C. 
     
     
       18. A process according to claim 15, 16 or 17 conducted in an inert reaction atmosphere. 
     
     
       19. A process according to claim 18 wherein the inert reaction atmosphere is argon. 
     
     
       20. A process according to claim 7 wherein the inert reaction atmosphere is argon.